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Could a new material involving a carbon nanotube and graphene hybrid put an end to the dendrite problem in lithium batteries? (Credit: Tour Group/Rice University)

The high energy capacity of lithium-ion batteries has led to them powering everything from tiny mobile devices to huge trucks. But current lithium-ion battery technology is nearing its limits and the search is on for a better lithium battery. But one thing stands in the way: dendrites. If a new technology by Rice University scientists lives up to its potential, it could solve this problem and enable lithium-metal batteries that can hold three times the energy of lithium-ion ones.

Dendrites are microscopic lithium fibers that form on the anodes during the charging process, spreading like a rash till they reach the other electrode and causing the battery to short circuit. As companies such as Samsung know only too well, this can cause the battery to catch fire or even explode.

“Lithium-ion batteries have changed the world, no doubt,” says chemist Dr. James Tour, who led the study. “But they’re about as good as they’re going to get. Your cellphone’s battery won’t last any longer until new technology comes along.”

For a start, it’s able to stop dendrite growth in its tracks. Key to it is a unique anode made from a material that was first created at the university five years ago. By using a covalent bond structure, it combines a two-dimensional graphene sheet and carbon nanotubes to form a seamless three-dimensional structure. As Tour explained back when the material was first unveiled:

“By growing graphene on metal (in this case copper) and then growing nanotubes from the graphene, the electrical contact between the nanotubes and the metal electrode is ohmic. That means electrons see no difference, because it’s all one seamless material.”

Envisioned for use in energy storage and electronics applications such as supercapacitors, it wasn’t until 2014, when co-lead author Abdul-Rahman Raji was experimenting with lithium metal and the graphene-nanotube hybrid, that the researchers discovered its potential as a dendrite inhibitor.

“I reasoned that lithium metal must have plated on the electrode while analyzing results of experiments carried out to store lithium ions in the anode material combined with a lithium cobalt oxide cathode in a full cell,” says Raji. “We were excited because the voltage profile of the full cell was very flat. At that moment, we knew we had found something special.”

Closer analysis revealed no dendrites had grown when the lithium metal was deposited into a standalone hybrid anode – but would it work in a proper battery?

To test the anode, the researchers built full battery prototypes with sulfur-based cathodes that retained 80 percent capacity after more than 500 charge-discharge cycles (i.e. the rough equivalent of what a cellphone goes through in a two-year period). No signs of dendrites were observed on the anodes.

How it works

The low density and high surface area of the nanotube forest allow the lithium metal to coat the carbon hybrid material evenly when the battery is charged. And since there is plenty of space for the particles to slip in and out during the charge and discharge cycle, they end up being evenly distributed and this stops the growth of dendrites altogether.

According to the study, the anode material is capable of a lithium storage capacity of 3,351 milliamp hours per gram, which is close to pure lithium’s theoretical maximum of 3,860 milliamp hours per gram, and 10 times that of lithium-ion batteries. And since the nanotube carpet has a low density, this means it’s able to coat all the way down to substrate and maximize use of the available volume.

“Many people doing battery research only make the anode,because to do the whole package is much harder,” says Tour. “We had to develop a commensurate cathode technology based upon sulfur to accommodate these ultrahigh-capacity lithium anodes in first-generation systems. We’re producing these full batteries, cathode plus anode, on a pilot scale, and they’re being tested.”

For certain frequencies of short-wave infrared light, most biological tissues are nearly as transparent as glass. Now, researchers have made tiny particles that can be injected into the body, where they emit those penetrating frequencies. The advance may provide a new way of making detailed images of internal body structures such as fine networks of blood vessels.

The new findings, based on the use of light-emitting particles called quantum dots, is described in a paper in the journal Nature Biomedical Engineering, by MIT research scientist Oliver Bruns, recent graduate Thomas Bischof PhD ’15, professor of chemistry Moungi Bawendi, and 21 others.

Near-infrared imaging for research on biological tissues, with wavelengths between 700 and 900 nanometers (billionths of a meter), is widely used, but wavelengths of around 1,000 to 2,000 nanometers have the potential to provide even better results, because body tissues are more transparent to that light. “We knew that this imaging mode would be better” than existing methods, Bruns explains, “but we were lacking high-quality emitters” — that is, light-emitting materials that could produce these precise wavelengths.

Light-emitting particles have been a specialty of Bawendi, the Lester Wolf Professor of Chemistry, whose lab has over the years developed new ways of making quantum dots. These nanocrystals, made of semiconductor materials, emit light whose frequency can be precisely tuned by controlling the exact size and composition of the particles.

The key was to develop versions of these quantum dots whose emissions matched the desired short-wave infrared frequencies and were bright enough to then be easily detected through the surrounding skin and muscle tissues. The team succeeded in making particles that are “orders of magnitude better than previous materials, and that allow unprecedented detail in biological imaging,” Bruns says. The synthesis of these new particles was initially described in a paper by graduate student Daniel Franke and others from the Bawendi group in Nature Communications last year.

The quantum dots the team produced are so bright that their emissions can be captured with very short exposure times, he says. This makes it possible to produce not just single images but video that captures details of motion, such as the flow of blood, making it possible to distinguish between veins and arteries.

The new light-emitting particles are also the first that are bright enough to allow imaging of internal organs in mice that are awake and moving, as opposed to previous methods that required them to be anesthetized, Bruns says. Initial applications would be for preclinical research in animals, as the compounds contain some materials that are unlikely to be approved for use in humans. The researchers are also working on developing versions that would be safer for humans.

The method also relies on the use of a newly developed camera that is highly sensitive to this particular range of short-wave infrared light. The camera is a commercially developed product, Bruns says, but his team was the first customer for the camera’s specialized detector, made of indium-gallium-arsenide. Though this camera was developed for research purposes, these frequencies of infrared light are also used as a way of seeing through fog or smoke.

Not only can the new method determine the direction of blood flow, Bruns says, it is detailed enough to track individual blood cells within that flow. “We can track the flow in each and every capillary, at super high speed,” he says. “We can get a quantitative measure of flow, and we can do such flow measurements at very high resolution, over large areas.”

Such imaging could potentially be used, for example, to study how the blood flow pattern in a tumor changes as the tumor develops, which might lead to new ways of monitoring disease progression or responsiveness to a drug treatment. “This could give a good indication of how treatments are working that was not possible before,” he says.

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The team included members from MIT’s departments of Chemistry, Chemical Engineering, Biological Engineering, and Mechanical Engineering, as well as from Harvard Medical School, the Harvard T.H. Chan School of Public Health, Raytheon Vision Systems, and University Medical Center in Hamburg, Germany. The work was supported by the National Institutes of Health, the National Cancer Institute, the National Foundation for Cancer Research, the Warshaw Institute for Pancreatic Cancer Research, the Massachusetts General Hospital Executive Committee on Research, the Army Research Office through the Institute for Soldier Nanotechnologies at MIT, the U.S. Department of Defense, and the National Science Foundation.

Control of ice growth kinetics. (A) Hexagonal ice composed by two basal facets (c-axis) and six prism facets (a-axis). (B) Random and aligned orientations of c-axes were found on trapezoid-shaped microgrooves (TMG) and V-shaped microgrooves (VMG) surfaces, respectively. (C) Ice embryos appear on the side walls, the edges, and the valleys of groove on TMG surfaces, resulting in different orientations of ice crystals. On the other hand, an ice embryo forms only at the valley of grooves on the VMG surface, leading to the confined ice orientation. Scale bars are 15 µm. (Reprinted with permission by American Chemical Society) (click on image to enlarge)

Researchers now have demonstrated the ability to spatially control frost nucleation (ice formation from water vapor) and to manipulate ice crystal growth kinetics.”The spatial control of icing in the condensation-freezing process and through the coating of hydrophilic materials has been demonstrated before,” Ming-Chang Lu, Associate Professor in the Department of Mechanical Engineering at National Chiao Tung University said, “However, the ice nucleation control and the confinement of ice crystal growth direction through manipulating roughness scale have not been reported in the literature.”

This motivated them to further explore whether the same control could be achieved in the icing process.Indeed, as they recently have reported in ACS Nano (“Control of Ice Formation”), they found that a surface’s anti-icing (preventing ice formation) and deicing performances could be promoted through the control of nucleation and the confinement of the ice crystal growth direction.The scientists achieved control of nucleation and the confinement of the crystal growth kinetics by manipulating local free energy barrier for nucleation.Moreover, the growth kinetics of ice can also be altered by adjusting the shape of the microgroove of the surface: Ice stacked along the direction of the V-shaped microgroove, whereas it grew in random directions on the trapezoid-shaped microgroove.As the researchers demonstrate in their paper, the spatial control of frost formation and the confinement of ice-growing kinetics improved the anti-icing and deicing performances.”We have shown that ice formation and ice crystal growth could be manipulated by tailoring surface roughness scale,” notes Lu.

“We believe that our results could be potentially applied to alleviate the icing issues in many industrial systems, such as, power transmission system, telecommunication system, heat exchangers, aircraft, etc.”In this work, the team systematically investigated – under an environmental scanning electron microscope (ESEM) – frosting and deicing processes on a plain silicon surface, a silicon nanowire (SiNW) array-coated surface, and V-shaped and trapezoid-shaped microgroove patterned surfaces.Nucleation is the first step of the phase transition during freezing. The team’s goal is to gain complete control of the ice formation process including nucleation, crystal growth, and ice spreading.”The results we demonstrated were on a Si surface and on a laboratory chip; in my opinion, the future directions are to explore whether the phenomena could be realized on other materials and on a larger system,” concludes Lu. “The ultimate goal is to have fully controls of icing and deicing processes. Therefore, it could be applied to alleviate the adverse effect caused by global warming, e.g., the loss of ice sheets.”

Quantum dots, or QDs, are semiconductor nanoparticles or nanocrystals, usually in the range of 2-10 nanometers (10-50 atoms) in size. Their small size and high surface-to-volume ratio affects their optical and electronic properties and makes them different from larger particles made of the same materials. Quantum dots confine the motion of conduction band electrons, valence band holes, or excitons (bound pairs of conduction band electrons and valence band holes) in all three spatial directions. Quantum dots are also sometimes referred to as ‘artificial atoms’, a term that emphasizes that they are a single object with bound, discrete electronic states, similarly to naturally occurring atoms or molecules.

Image: Grapehene Quantum Dots

Many types of quantum dot are fluorescent – they emit light of specific frequencies if electricity or light is applied to them. These frequencies can be tuned by changing the dots’ size, shape and material, opening the door to diverse applications. Generally speaking, smaller dots appear blue while larger ones tend to be more red. Specific colors also vary depending on the exact composition of the QD.Applications

Thanks to their highly tunable properties, QDs are attracting interest from various application developers and researchers. Among these potential applications are displays, transistors, solar cells, diode lasers, quantum computing, and medical imaging. Additionally, their small size enables QDs to be suspended in solution, which leads to possible uses in inkjet printing and spin-coating. These processing techniques may result in less-expensive and less time consuming methods of semiconductor fabrication. Quantum dots are considered especially suitable for optical applications, thanks to their ability to emit diverse colors, coupled with their high efficiencies, longer lifetimes and high extinction coefficient.

Their small size also means that electrons do not have to travel as far as with larger particles, thus electronic devices can operate faster. Examples of applications that take advantage of these electronic properties include transistors, solar cells, quantum computing, and more. QDs can greatly improve LED screens, offering them higher peak brightness, better colour accuracy, higher color saturation and more. QDs are also very interesting for use in biomedical applications, since their small size allows them to travel in the body, thus making them suitable for applications like medical imaging, biosensors, etc.

What is graphene?

Graphene is a material made of carbon atoms that are bonded together in a repeating pattern of hexagons. Graphene is so thin that it is considered two dimensional. Graphene’s flat honeycomb pattern gives it many extraordinary characteristics, such as being the strongest material in the world, as well as one of the lightest, most conductive and transparent. Graphene has endless potential applications, in almost every industry (like electronics, medicine, aviation and much more).

Graphene structure photo
The single layers of carbon atoms provide the basis for many other materials. Graphite, like the substance found in pencil lead, is formed by stacked graphene. Carbon nanotubes are made of rolled graphene and are used in many emerging applications from sports gear to biomedicine.

Graphene quantum dots

The term graphene quantum dots (GQDs) is usually used to describe miniscule fragments, limited in size, or domains, of single-layer to tens of layers of graphene. GQDs often possess properties like low toxicity, stable photoluminescence, chemical stability and pronounced quantum confinement effect, which make them attractive for biological, opto-electronics, energy and environmental applications.

Photo: Dr. James M. Tour: Rice University:

The synthesis of graphene quantum structures, such as graphene quantum dots, has become a popular topic in recent years. While graphene usually does not have a bandgap – which is a problem for many applications – graphene quantum dots do contain a bandgap due to quantum confinement and edge effects, and that bandgap modifies graphene’s carrier behaviors and can lead to versatile applications in optoelectronics. GQDs were also found to have four quantum states at a given energy level, unlike semiconductor quantum dots, which have only two. These additional quantum states, according to researchers, could make GQDs beneficial for quantum computing.
Additional properties of GQDs such as high transparency and high surface area have been proposed for energy and display applications. Because of the large surface area, electrodes using GQDs are applied for capacitors and batteries. Various techniques have been developed to produce GQDs. Top-down methods include solution chemical, microwave, and ultrasonic methods. Bottom-up methods include hydrothermal and electrochemical methods.

Graphene Quantum Dots in the News

Dotz Nano secures first order of graphene quantum dots:

In January 2017, Dotz Nano, a nanotechnology company focused on the development, manufacture and commercialization of graphene quantum dots (GQDs), signed a marketing agreement with Strem Chemicals, a manufacturer and distributor of specialty chemicals headquartered in the U.S.

Strem Chemicals will aim to facilitate sales of Dotz’s GQDs to academic, industrial and government research and development laboratories, as well as commercial businesses using GQDs for research purposes.

Fuji Pigment announces graphene and carbon QD manufacturing process:

In April 2016, Fuji Pigment announced the development of a large-scale manufacturing process for carbon and graphene quantum dots (QDs). Fuji Pigment stated that its toxic-metal-free QDs exhibit a high light-emitting quantum efficiency and stability comparable to the toxic metal-based quantum dots.

Samsung developed graphene quantum dots based flash memory devices:

In June 2014, researchers from Samsung Electronics (and Korea’s Kyung Hee University) developed flash devices based on graphene quantum dots (GQDs). The performance of such a device is promising, with an electron density that is comparable to semiconductor and metal nanocrystal based memories. Those flash memory can also be made flexible and transparent.

PEG-PDI, which incorporates a compound long used as a red dye, changes to greenish-blue with the addition of potassium superoxide as it converts the superoxide to dioxygen. Adding more further quenches the reactive oxygen species superoxide, turning the solution purple. Adding hydrogen peroxide in the last step clarifies the liquid, showing that a build-up of excess hydrogen peroxide can deactivate the structure. PEG-PDI, created at Rice University, shows potential as a biological antioxidant. Credit: Tour Group/Rice University

Treated particles of graphene derived from carbon nanotubes have demonstrated remarkable potential as life-saving antioxidants, but as small as they are, something even smaller had to be created to figure out why they work so well.

Researchers at Rice University, the McGovern Medical School at the University of Texas Health Science Center at Houston (UTHealth) and Baylor College of Medicine created single-molecule compounds that also quench damaging reactive oxygen species (ROS) but are far easier to analyze using standard scientific tools. The molecules may become the basis for new antioxidant therapies in their own right.

The research appears in the American Chemical Society journal ACS Nano.

The original compounds are hydrophilic carbon clusters functionalized with polyethylene glycol, known as PEG-HCCs and created by Rice and Baylor scientists five years ago. The particles help neutralize ROS molecules overexpressed by the body’s cells in response to an injury before they damage cells or cause mutations.

PEG-HCCs show promise for treating cancer, rebooting blood flow in the brain after traumatic injury and controlling chronic diseases.

The new particles, called PEG-PDI, consist of polyethylene glycol and perylene diimide, a compound used as a dye, the color in red car paint and in solar cells for its light-absorbing properties. Their ability to accept electrons from other molecules makes them functionally similar to PEG-HCCs.

They’re close enough to serve as an analog for experiments, according to Rice chemist James Tour, who led the study with University of Texas biochemist Ah-Lim Tsai.

The researchers wrote that the molecule is not only the first example of a small molecular analogue of PEG-HCCs, but also represents the first successful isolation of a PDI radical anion as a single crystal, which allows its structure to be captured with X-ray crystallography.

“This allows us to see the structure of these active particles,” Tour said. “We can get a view of every atom and the distances between them, and get a lot of information about how these molecules quench destructive oxidants in biological tissue.

“Lots of people get crystal structures for stable compounds, but this is a transient intermediate during a catalytic reaction,” he said. “To be able to crystallize a reactive intermediate like that is amazing.”

The crystal structure of PEG-PDI is achieved using cobaltocene as a reducing agent and omitting solvents and hydrogen atoms for clarity. Carbon atoms are gray, nitrogens are blue, oxygens red and cobalts purple. The molecules created by scientists at Rice University, the McGovern Medical School at the University ofTexas Health Science Center at Houston and Baylor College of Medicine are efficient antioxidants and help scientists understand how larger nanoparticles quench damaging reactive oxygen species in the body. Credit: Tour Group

PEG-HCCs are about 3 nanometers wide and 30 to 40 nanometers long. By comparison, much simpler PEG-PDI molecules are less than a nanometer in width and length.

Testing the PEG-PDI molecules can be as simple as putting them in a solution that contains reactive oxygen species molecules like potassium superoxide and watching the solution change color. Further characterization with electron paramagnetic resonance spectroscopy was more complicated, but the fact that it’s even possible makes them powerful tools in resolving mechanistic details, the researchers said.

Tour said adding polyethylene glycol makes the molecules soluble and also increases the amount of time they remain in the bloodstream. “Without PEG, they just go right out of the system through the kidneys,” he said.

When the PEG groups are added, the molecules circulate longer and continue to catalyze reactions.

He said PEG-PDI is just as effective as PEG-HCCs if measured by weight. “Because they have so much more surface area, PEG-HCC particles probably catalyze more parallel reactions per particle,” Tour said. “But if you compare them with PEG-PDI by weight, they are quite similar in total catalytic activity.”

Understanding the structure of PEG-PDI should allow researchers to customize the molecule for applications. “We should have a tremendous ability to modify the molecule’s structure,” he said. “We can add anything we want, exactly where we want, for specific therapies.”

The researchers said PEG-PDI may also be efficient metal- and protein-free catalysts for oxygen reduction reactions used in industry and essential to fuel cells. They are intrinsically more stable than enzymes and can function in much a wider pH range, Tsai said.

Co-author Thomas Kent, a professor of neurology at Baylor who has worked on the project from the start, noted small molecules have a better chance to get on the fast track to approval for therapy by the Food and Drug Administration than nanotube-based agents.
“A small molecule that is not derived from larger nanomaterial may have a better chance of approval to use in humans, assuming it is safe and effective,” he said.

Tour said PEG-PDI serves as a precise model for other graphene derivatives like graphene oxide and permits a more detailed study of graphene-based nanomaterials.

“Making nanomaterials smaller, from well-defined molecules, permits 150 years of synthetic chemistry methods to address the mechanistic questions within nanotechnology,” he said.

Rice University researchers who pioneered the development of laser-induced graphene have configured their discovery into flexible, solid-state microsupercapacitors that rival the best available for energy storage and delivery.

The devices developed in the lab of Rice chemist James Tour are geared toward electronics and apparel. They are the subject of a new paper in the journal Advanced Materials.

Microsupercapacitors are not batteries, but inch closer to them as the technology improves. Traditional capacitors store energy and release it quickly (as in a camera flash), unlike common lithium-ion batteries that take a long time to charge and release their energy as needed.

Researchers at Rice University in Houston, Texas, have developed a nanoporous material that has the energy density (the amount of energy stored per unit mass) of an electrochemical battery and the power density (the maximum amount of power that can be supplied per unit mass) of a supercapacitor. It’s important to note that the energy storage device enabled by the material is not claimed to be either of these types of energy storage devices.

The research community has wearied of claims that some new nanomaterial enables a “supercapacitor,” when in fact the energy storage device is not a supercapacitor at all, but a battery. However, in this case, the Rice University researchers, led by James Tour, who is known for having increased the storage capacity of lithium-ion (Li-ion) batteries with graphene, don’t make any claims that the device they created is a supercapacitor. Instead it is described as an electrochemical capacitor with nanoporous nickel-fluoride electrodes layered around a solid electrolyte that is flexible and relatively easy to scale up for manufacturing.

The issue of appropriate nomenclature aside, the reported performance figures for this energy storage material are very attractive. In the Journal of the American Chemical Society (“Flexible Three-Dimensional Nanoporous Metal-Based Energy Devices“), the researchers report energy density of 384 watt-hours per kilogram (Wh/kg), and power density of 112 kilowatts per kilogram (kW/kg).

To give some context to these numbers, a typical energy density for a Li-ion battery is 200Wh/kg, whereas commercially available supercapacitors store around 5- to 25 Wh/kg and research prototype supercapacitors have made claims of anywhere from 85 to 164 Wh/kg. In terms of power density, the numbers for the new nanoporous material is in line with those of supercapacitors, which range from 10 to 100 kW/kg—far higher than the 0.005 to 0.4kW/kg that batteries can deliver.

“The numbers are exceedingly high in the power that it can deliver, and it’s a very simple method to make high-powered systems,” Tour said in a press release. “We’re already talking with companies interested in commercializing this.”

To make the battery-supercapacitor hybrid, the Rice team deposited a nickel layer on a backing material. They then etched the nickel layer to create pores five nanometers in diameter. The result is high surface area for storing ions. After removing the backing, the nickel-based electrode material is wrapped around a solid electrolyte of potassium hyrodroxide in polyvinyl alcohol. In testing, the researchers found that there was no degradation of the pore structure after 10 000 charge-discharge cycles, or any significant degradation of the electrode-electrolyte interface.

“Compared with a lithium-ion device, the structure is quite simple and safe,” said Yang Yang, lead author of the paper, in the press release. “It behaves like a battery but the structure is that of a supercapacitor. If we use it as a supercapacitor, we can charge quickly at a high current rate and discharge it in a very short time. But for other applications, we find we can set it up to charge more slowly and to discharge slowly like a battery.”

With the device’s flexibility and high charge-up rate, it’s possible to imagine this storage device powering flexible mobile devices. However, charging rates for the battery/supercapacitor will be limited by the typical 200-amp 240V single-phase residential service, which is only capable of providing (absent any other load) only 48 kW.

Rice University scientists advanced their recent development of laser-induced graphene (LIG) by producing and testing stacked, three-dimensional supercapacitors, energy-storage devices that are important for portable, flexible electronics.

The Rice lab of chemist James Tour discovered last year that firing a laser at an inexpensive polymer burned off other elements and left a film of porous graphene, the much-studied atom-thick lattice of carbon. The researchers viewed the porous, conductive material as a perfect electrode for supercapacitors or electronic circuits.

To prove it, members of the Tour group have since extended their work to make vertically aligned supercapacitors with laser-induced graphene on both sides of a polymer sheet. The sections are then stacked with solid electrolytes in between for a multilayer sandwich with multiple microsupercapacitors.

A schematic shows the process developed by Rice University scientists to make vertical microsupercapacitors with laser-induced graphene. The flexible devices show potential for use in wearable and next-generation electronics. (Courtesy of the Tour Group)

The flexible stacks show excellent energy-storage capacity and power potential and can be scaled up for commercial applications. LIG can be made in air at ambient temperature, perhaps in industrial quantities through roll-to-roll processes, Tour said.

Capacitors use an electrostatic charge to store energy they can release quickly, to a camera’s flash, for example. Unlike chemical-based rechargeable batteries, capacitors charge fast and release all their energy at once when triggered. But chemical batteries hold far more energy. Supercapacitors combine useful qualities of both – the fast charge/discharge of capacitors and high-energy capacity of batteries – into one package.

LIG supercapacitors appear able to do all that with the added benefits of flexibility and scalability. The flexibility ensures they can easily conform to varied packages – they can be rolled within a cylinder, for instance – without giving up any of the device’s performance.

“What we’ve made are comparable to microsupercapacitors being commercialized now, but our ability to put devices into a 3-D configuration allows us to pack a lot of them into a very small area,” Tour said. “We simply stack them up.

“The other key is that we’re doing this very simply. Nothing about the process requires a clean room. It’s done on a commercial laser system, as found in routine machine shops, in the open air.”

An electron microscope image shows the cross section of laser-induced graphene burned into both sides of a polyimide substrate. The flexible material created at Rice University has the potential for use in electronics or for energy storage. (Courtesy of the Tour Group)

Ripples, wrinkles and sub-10-nanometer pores in the surface and atomic-level imperfections give LIG its ability to store a lot of energy. But the graphene retains its ability to move electrons quickly and gives it the quick charge-and-release characteristics of a supercapacitor. In testing, the researchers charged and discharged the devices for thousands of cycles with almost no loss of capacitance.

To show how well their supercapacitors scale up for applications, the researchers wired pairs of each variety of device in serial and parallel. As expected, they found the serial devices delivered double the working voltage, while the parallels doubled the discharge time at the same current density.

The vertical supercapacitors showed almost no change in electrical performance when flexed, even after 8,000 bending cycles.

Tour said that while thin-film lithium ion batteries are able to store more energy, LIG supercapacitors of the same size offer three times the performance in power (the speed at which energy flows). And the LIG devices can easily scale up for increased capacity.

“We’ve demonstrated that these are going to be excellent components of the flexible electronics that will soon be embedded in clothing and consumer goods,” he said.

Like this:

The best material to keep carbon dioxide from natural gas wells from fouling the atmosphere may be a derivative of asphalt, according to Rice Univ. scientists.

The Rice laboratory of chemist James Tour followed up on last year’s discovery of a “green” carbon capture material for wellhead sequestration with the news that an even better compound could be made cheaply in a few steps from asphalt, the black, petroleum-based substance primarily used to build roads.

The research appears in Applied Materials and Interfaces.

The best version of several made by the Tour lab is a powder that holds 114% of its weight in carbon dioxide. Like last year’s material, these new porous carbon materials capture carbon dioxide molecules at room temperature while letting the desired methane natural gas flow through.

Each grain of a powder drawn from asphalt has the ability to capture more than its own weight in carbon dioxide under pressure. The material invented at Rice Univ. is intended to separate carbon dioxide from streams at natural gas wellheads. Image: Jeff Fitlow

The basic compound known as asphalt-porous carbon (A-PC) captures carbon dioxide as it leaves a wellhead under pressure supplied by the rising gas itself (about 30 atmospheres, or 30 times atmospheric pressure at sea level). When the pressure is relieved, A-PC spontaneously releases the carbon dioxide, which can be piped off to storage, pumped back downhole or repurposed for such uses as enhanced oil recovery.

“This provides an ultra-inexpensive route to a high-value material for the capture of carbon dioxide from natural gas streams,” Tour said. “Not only did we increase its capacity, we lowered the price substantially.” He said they tried many grades of asphalt, some costing as little as 30 cents per pound.

Tour’s goal is to simplify the process of capturing carbon from wellheads at sea, where there’s limited room for bulky equipment. The ability of A-PC to capture and release carbon over many cycles without degrading makes it practical, he said.

The paper’s lead authors, postdoctoral associate Almaz Jalilov and graduate student Gedeng Ruan, and their Rice colleagues made A-PC by mixing asphalt with potassium hydroxide at high temperature; they turned it into a porous carbon with a lot of surface area: 2,780 square meters per gram. That material captured 93% of its weight in carbon dioxide. Further experiments showed processing A-PC with ammonia and then hydrogen increased its capacity to 114%.

Tour said the lab is continuing to tweak the material but noted that it’s already better for carbon capture than other materials in current use. Amine-based materials now used by industrial facilities like power plants to absorb carbon dioxide are expensive and corrosive and can only capture about 13% carbon dioxide by weight. Materials in development based on metal organic frameworks are far more expensive to produce and don’t show as great a selectivity for carbon dioxide over methane, he said.

Researchers at Rice University have created flexible, patterned sheets of multilayer graphene from a cheap polymer by burning it with a computer-controlled laser. The process works in air at room temperature and eliminates the need for hot furnaces and controlled environments, and it makes graphene that may be suitable for electronics or energy storage.

Under a microscope, what the researchers call laser-induced graphene (LIG) doesn’t look like a perfect chicken wire-like grid of atoms. Instead, it’s a jumble of interconnected graphene flakes with five-, six- and seven-atom rings. The paired five- and seven-atom rings are considered defects – but in this case, they’re not. They’re features.

The material can be made in detailed patterns. For show-and-tell, the Rice team patterned millimeter-sized LIG Owls (the school’s mascot), and for practical testing they fabricated microscale supercapacitors with LIG electrodes in one-step scribing.

The labs of Rice chemist James Tour and theoretical physicist Boris Yakobson published their research online today in Nature Communications.

The one-step process is scalable, said Tour, who suggested it could allow for rapid roll-to-roll manufacture of nanoscale electronics.

“This will be good for items people can relate to: clothing and wearable electronics like smartwatches that configure to your smartphone,” he said.

This top-down approach to making graphene is quite different from previous works by Tour’s lab, which pioneered the small-scale manufacture of the atom-thick material from common carbon sources, even Girl Scout cookies, and learned to split multiwalled nanotubes into useful graphene nanoribbons.

But as in the previous work, the base material for LIG is inexpensive. “You buy polyimide flexible plastic sheets in huge rolls, called Kapton, and the process is done entirely in air with a rapid writing process. That sets it up for a very scalable, industrial process,” Tour said.

Graphene microsupercapacitors were created in polymer with a laser at Rice University’s Oshman Engineering Design Kitchen. The room-temperature process makes graphene that may be suitable for electronics or energy storage. Credit: Tour Group/Rice University

The product is not a two-dimensional slice of graphene but a porous foam of interconnected flakes about 20 microns thick. The laser doesn’t cut all the way through, so the foam remains attached to a manageable, insulating, flexible plastic base.

The process only works with a particular polymer. The researchers led by Jian Lin, a former postdoctoral research in the Tour Group and now an assistant professor at the University of Missouri, tried 15 different polymers and found only two could be converted to LIG. Of those, polyimide was clearly the best.

Tour said the resulting graphene isn’t as conductive as copper, but it doesn’t need to be. “It’s conductive enough for many applications,” he said.

He said LIG can easily be turned into a supercapacitor, which combines the fast-charging, power-storing capacity of a capacitor with the higher energy-delivering capability, though not yet as high as in a battery. The defects could be the key, Tour said.

A scanning electron microscope shows a close-up of laser-induced graphene foam produced by researchers at Rice University. The scale bar for the main image is 10 microns; the bar for the inset is 1 micron. Credit: Tour Group/Rice University

“A normal sheet of graphene is full of six-member rings,” he said. “Once in a while you see a meandering line of 5-7s, but this new material is filled with 5-7s. It’s a very unusual structure, and these are the domains that trap electrons. Had it just been normal (highly conductive) graphene, it couldn’t store a charge.”

Calculations by Yakobson’s group showed that these balancing five-and-seven formations make the material more metallic and enhance its ability to store charges.

This finely detailed Rice Owl was produced by burning a graphene foam pattern into a flexible polyimide sheet with a laser. The multilayered graphene that results from the process may be suitable for energy storage or electronics. The scale …more

“Theoretical methods and density functional computations allowed us to look inside the electronic energy states’ organization,” Yakobson said. “What we discovered is that the very low density of available states—which is crucial for the layer capacitance—increases dramatically, due to various topological defects, mainly pentagonal and heptagonal rings.

“The fact that highly defective graphene performs so well is a freebie, a gift from nature,” he said.

Miguel José Yacaman, chairman of the Department of Physics at the University of Texas at San Antonio, contributed his expertise in transmission electron microscope imaging to confirm the existence of so many defects.

A Rice University lab is using a laser to write graphene microsupercapacitors in a common polymer material. The laser removes nearly everything but carbon from a 20-micron layer, leaving behind porous graphene foam that may be suitable for …more

“We have what is called aberration-corrected microscopy, which allows us to see the defects,” Yacaman said. “The resolution is below 1 angstrom, basically 70 picometers (trillionths of a meter), and that’s what you need to really look at single atoms.”

Tour’s lab used the machine shop lasers at Rice’s Oshman Engineering Design Kitchen to create their robust microsupercapacitors. The best results showed capacitance of more than 4 millifarads per square centimeter and power density of about 9 milliwatts per square centimeter, comparable to other carbon-based microsupercapacitors, and negligible degradation after as many as 9,000 charge/discharge cycles. This capacitance is sufficient for inexpensive wearable electronic devices, and Tour said his group continues to make improvements.

He said the lab didn’t start out looking for LIG. “Everything converged. Nature can be a hard taskmaster, but once in a while, she gives you something much better than what you had asked for. Or expected.”